Water soluble aminoanthraquinone hair dyes



United States Patent 8 Claims. cl. 167-88) ABSTRACT OF THE DISCLOSURE IHair dyeing agents applicable at room temperature and resistant tofading. The agents are based on substituted aminoanthraquinones, wherebythe substituents render the compounds water-soluble. Methods for theproduction of the agents are described.

The invention relates to agents for dyeing of human hair and, moreparticularly, to dyeing agents based on anthraquinone of a constitutionwhich permits their application substantially at room temperature.

The employment of so-called oxidation dyes which contain aromaticdiamines or polyphenols for dyeing of human hair is known. These dyeshave the disadvantage that they must be developed with the aid ofoxidizers, such as H 0 or perborates.

It therefore has been attempted to use hair dyes containing directlyacting dyes, e.g., anthraquinone derivatives which are substituted inthe nucleus by amino-, hydroxyl-, carboxylor sulfo groups.

In the practical application of these anthraquinone compounds known fordyeing of human hair dyeing at temperatures ranging from 40 to 60 C. isrequired. It therefore becomes necessary to use heating caps and similardevices on the human head to attain the required temperatures. Moreover,the hitherto known anthraquinone hair dyes are difficultly soluble sothat they had been employed solely as dispersion. dyes.

It now has been found that the drawbacks named above are not encounteredwith the agents according to the instant invention. Therein,amino-anthraquinone dyes are employed having the generic Formulae 1and/or 2;

lTIHz O l IHz i) I' IX R r 1I;

wherein R is hydrogen or an alkyl group having 1-3 carbon atoms, and Xis an aliphatic group having 1-6 carbon atoms or else a phenyl groupcontaining a further group rendering the compound water-soluble.

Of the anthraquinone dyestuifs to be considered for the purpose, thoseare especially suited which contain 3,368,942 Patented Feb. 13, 1968 awater-soluble group such as SO H, -OH or COOH. It is understood that thecorresponding alkalior ammonium salts and also the monoanddiethanolamino salts can be employed equally well.

Compounds of the kind named above can be produced e.g., by reacting1,4-diamino-S-nitroanthraquinone or 2- chloro-1,4-diaminoanthraquinonewith such compounds as aminobenzoic acid, sulfanilic acid or suchaminocarboxylic acids as alphaor betaalanine. Aminoalkylsulfonic acids,such as taurine or N-methyltaurine, also can be used. The reactions arecarried out in the presence of solid alkali hydroxide in solvents suchas nitrobenzene.

The dyes can be mixed with any desired wetting, dispersing and washingagents, especially those of anionic or nonionic character. Particularlyto be considered are alkylbenzene sulfonates, fatty alcohol sulfates,alkyl sulfonates, fatty acid ethanolamides, ethylene adducts on fattyacids and fatty alcohols.

The dyeability of the dyeing agents named above remains good even inmixture with the wetting or washing agents. This facilitates theproduction of the hair dyeing agents in the form of shampoos, especiallyof cream shampoos. The latter often are desired in practice.

Furthermore, thickeners may be added to the agents according to theinvention e.g., methylcellulose, starch, higher fatty alcohols,Vaseline, parafiin oil, fatty acids; also essential oils and hairgrooming agents, such as pantothenic acid or cholesterol.

The additives named are admixed in the commonly used quantities. Wettingor dispersing agents are present in qantities of 0.5-30 percent byweight, thickeners in amounts of 0.1-25 percent by weight, calculated onthe total composition. The concentration of the dyes them selves amountsto up to 5 percent by weight, but preferably 0.1 to 2 percent, of thetotal composition.

Finally, permanent waving agents, known per se, may be added to thenovel hair dyeing agents. These waving agents are based on compoundscontaining mercapto groups, e.g., thioglycolic acid, thiolactic acid,mercaptopropaneor mercaptobutanesulfonic acid. The hair dyeing agentsmay be produced containing these additives since the dyestuffs arestable in their presence.

The new hair dyeing agents allow dyeing of human hair without resortingto heating caps or similar devices since they are applied attemperatures below 40 C., and preferably at room temperature. Their pHmay range from 7 to 10, preferably from 8.5 to 9.5. The agents may Iserve for coloring gray hair or for applying a new color to any colorhair. The hair thus dyed is extremely resistant to fading due to washingor friction, e.g., rubbing. When a permanent wave is applied to hairthus dyed, a change in the color or hue does not occur. The dyes fixwell on human hair and, in any of the mixtures described above, can bestored practically indefinitely.

The invention now will be further explained by the following examples.

However, it should be understood that these are given merely by way ofillustration, and not of limitation, and that numerous changes may bemade in the details without departing from the spirit and the scope ofthe invention as hereinafter claimed.

All parts given in the examples are parts by weight.

Example 1 11.4 parts 1,4-diamino-S-nitroanthraquinone, 11 partsN-methyltaurine and 0.8 part powdered NaOH were mixed into 60 partsnitrobenzene and the temperature held at 50 C. for one-half hour. Afterthat, the mixture was heated at C. for 12 hours. The reaction mixturethen was refined by separating the nitrobenzene and alkali.

The dye thus obtained had the Formula 3 and imparted to gray hair astrong blue color with a purplish hue when applied for 20 minutes at 25C. in an ammonia solution of a pH of 9.5.

Example 2 8 parts of a fatty alcohol mixture (C -C and 10 parts fattyalcohol sulfate (C -C were heated to 90 C. and emulsified with 60 partswater. Into this emulsion the dye obtained as described in Example 1,together with 1 part NH OH and 8 parts water, were stirred. A cream thuswas obtained having a pH of substantially 9.5. This cream, applied tonaturally gray hair, dyed the same purple-blue at room temperature. Thehair had a strong hue and did not discolor upon washing.

Example 3 Hair of red color is obtained when the cream described inExample 2, in lieu of the dye used therein, contains an anthraquinonedye of Formula 4:

O NHa II mNQSOsH H I O NH2 Example 4 10 parts fatty alcohol (C -C 2parts wool fat, and 12 parts fatty alcohol sulfate (C -C were heated to98 C., and 1 part of an anthraquinone dye of Formula 5 added:

l N112 d HN0 o n The mixture then was emulsified in 75 parts water andcooled to room temperature under agitation. The pH of the cream wasadjusted to 8. This cream dyed naturally gray hair purple-blue at roomtemperature within a treatment time of 20 minutes.

A similar hair color was obtained by incorporating, in lieu of dye (5),dye (6) of the following constitution:

NHz O I II NH: O HN-CHPCHz-COONH (6) Example 5 1 part anthraquinone dyeof Formula 7 was incorporated in a shampoo cream. The latter had beenproduced by heating a mixture of 4.5 parts cetyl alcohol, 4.5 partsstearyl alcohol, 1.5 parts fatty alcohol mixture (C -C and 10 partsfatty alcohol sulfate (C -C to 98 C., addition of the dye andemulsification with 78 parts water. The pH of the cream was adjusted to9.5 with ammonia.

4 Naturally grey hair treated with this cream at room temperature,assumed a mauve color within 20 minutes.

Example 6 Hair of red color is obtained when the cream described inExample 5, in lieu of the dye used therein, contains an anthraquinonedye of Formula 8:

(I) NH2 This dye is produced by reacting2-chloro-l,4-diaminoanthraquinone with (omega)-amino-heptylic acid. Thereaction is carried out in the presence of solid potassium hydroxide andin solvents such as xylene.

Example 7 1 part of anthraquinone dye of formula ([JaHr IIIII: El)lTI-OHz-CHa-S 03H was mixed into a hair cream as described in Example 5,except that the pH was adjusted to 8.5. This cream dyed naturally greyhair blue at room temperature within a treatment of 15 minutes. The dyeis produced by reacting l,4-diamino-5-nitroanthraquinone withN-propyl-taurin in presence of solid NaOH and nitrobenzene as solvent.

The times named in the preceding examples for application of the agentsmerely are illustrative, and application times of 15 to 30 minutes canbe employed.

Example 8 14.1 parts of 1,4-diamino-5-nitr0anthraquinone and 50 partsmonoethanolamine were mixed and the temperature held at 70 C. for 15hours under stirring. After that, the surplus of monoethanolamine wasdistilled in vacuo, thereafter 50 parts water were added and thereaction mixture neutralized with aqueous HCl, filtered and the residuewas dried at C. in vacuo. The dye thus obtained had the Formula 10 IIHI:O IIQHCIDCIIZQH wherein R is selected from the group consisting ofhydrogen and alkyl having 1 to 3 carbon atoms; and X is selected fromthe group consisting of alkylene of 1 to 6 carbon atoms and phenyl, saidalkylene and phenyl having an end group selected from sulfo-,hydroxyland carboxyl, and their alkali metal, ammonium, monoanddiethanolamine salts.

2. The agents as defined in claim 1, wherein X is (CH SO H 3. The agentsas defined in claim 1, wherein X is 4. The agents as defined in claim 1,wherein X is 5. The agents as defined in claim 1, wherein X is (CH2)2OH6. The agents as defined in claim 1, wherein said compounds areincorporated in amounts from 0.1 to 5 percent by weight, calculated onthe total composition, in a cream composed of substances selected fromthe group consisting of nonionic and anionic surfactants, thickeners,essential oils, hair grooming agents, permanent Waving agents, andmixtures thereof.

7. A process for the dyeing of human hair which comprises applying tosaid hair for approximately 15 to 30 minutes and substantially at roomtemperature a cream having as active dyeing ingredient an efiYectiveamount of a compound selected from the group consisting of NH2 0 I lland I OI NH2 wherein R is selected from the group consisting of hydrogenand alkyl having 1-3 carbon atoms, and X is selected from the groupconsisting of alkylene of 1 to 6 carbon atoms and phenyl, said alkyleneand phenyl having an end group selected from sulfo, hydroxyl andcarboxyl, and their alkali metal, ammonium, monoand diethanolaminesalts.

8. A process for the dyeing of human hair which comprises applying tosaid hair for approximately 15 to 30 minutes and substantially at roomtemperature a cream having as active dyeing ingredient 0.1 to 5 percentby weight, calculated on total composition, of a compound selected fromthe group consisting of r t" t w I'QX and I Y Y 1 NH2 0 IIIX O NHzReferences Cited UNITED STATES PATENTS 2,730,534 1/1956 Hoefle et al.260374 X 3,168,441 2/1965 Bil et al. 167-88 3,253,876 5/1966 Wilcox eta1 839 X ALBERT T. MEYERS, Primary Examiner.

V. C. CLARKE, Assistant Examiner.

